Red or bluish-red fiber-reactive monoazo compound having 7-substituted amino-1-naphthol-sulfonic acid as coupling component between the chromophore and fiber reactive portions of the compound

ABSTRACT

A monoazo compound of the following formula in a free acid form, ##STR1## wherein R 1 , R 2  and R 4  are independently hydrogen or lower alkyl, R 3  is lower alkyl, acyl or (sulfo)- phenyl, R 5  is hydrogen or sulfo, B is (sulfo)phenylene or sulfonaphthylmethylene, X is chlorine, fluorine, phenoxy or (substituted)amino, A is (substituted)phenylene or (substituted)naphthylene, and Z is --SO 2  CH═CH 2  or --SO 2  CH 2  CH 2  Y in which Y is a splittable group by the action of an alkali, which meets requirements of high degree in a dye industry with respect to dyeing properties such as build-up property and fastness properties such as formalin fastness, formalin-light fastness.

The present invention relates to a fiber-reactive monoazo compoundhaving a 7-susbstituted amino-1- naphthol mono-or di-sulfonic acid as acoupling component, production thereof and application thereof fordyeing and printing fiber materials.

Various kinds of fiber-reactive dyes have heretofore been used fordyeing or printing fiber materials. Of these, reactive dyes having bothmonohalogenotriazinyl group and vinylsulfone type group such assulfatoethyl-sulfonyl group in one molecule are prominent because oftheir improved dye performances. As reactive dyes of this kind usefulfor dyeing or printing fiber materials in red color, for example, amonoazo compound having the following formula, ##STR2## is disclosed inPublished Unexamined Japanese Patent Application No. 199877/1982.However, known red dyes of this kind including the compound of the aboveformula are not yet satisfactory to meet the requirements of high degreewith respect to dyeing properties such as build-up property,insusceptibility to changes in dyeing temperature and the like as wellas fastness properties such as formalin fastness, foralin-light fastnessand the like, and therefore they wait for a still further improvement ofsuch dye performances.

The present inventors have undertaken extensive studies to find monoazocompounds meeting the afore-mentioned requirements, and attained to thepresent invention.

The present invention provides a monoazo compound of the followingformula (I), or a salt thereof, ##STR3## wherein R₁ and R₂ independentlyof one another denote hydrogen or unsubstituted or substituted loweralkyl, R₃ denotes unsubstituted or substituted lower alkyl, acyl or agroup of the formula, ##STR4## R₄ denotes hydrogen or unsubstituted orsubstituted lower alkyl, and R₅ denotes hydrogen or sulfo, B denotes agroup of the formula, ##STR5## in which R₆ is hydrogen, chloride, sulfo,carboxy, methyl, methoxy or ethoxy, or a group of the formula, ##STR6##X denotes chloride, fluorine, lower alkoxy, unsubstituted or substitutedphenoxy, or a group of the formula, ##STR7## in which R₇ and R₈independently of one another are hydrogen or an unsubstituted orsubstituted lower alkyl, phenyl, naphtyl or benzyl group, A denotes anunsubstituted or substituted phenylene or napthylene group, and Zdenotes a group of the formula, --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Y, is agroup splittable by the action of an alkali, and a process for producingthe monoazo compound of the formula (I), which comprises (a) reacting adiazonium salt of an amine compound of the following the formula (IV),##STR8## wherein R₁, R₂, A, B and Z are defined above, and X₁ denoteschloride of fluorine, with a naphthol compound of the following formula(V), ##STR9## wherein R₃, R₄ and R₅ are as defined above, or reactingany one of an aromatic amine compound of the following formula (III),##STR10## wherein R₁, A and Z are as defined above, or a monoazanaphthol compound of the following formula (VII), ##STR11## wherein R₂,R₃, R₄, R₅ and B are as defined above, with cyanuric chloride orcyanuric fluoride, followed by the reaction with the remaining one, toobtain a monoazo compound of the following formula (I'), ##STR12##wherein R₁, R₂, R₃, R₄, R₅, A, B, X₁ and Z are as defined above, whichcorresponds to the monoazo compound of the formula (I) having chlorineor fluorine as X, or (b) reacting the monoazo compound of the formula(I') with a compound of the following formula (VIII),

    H--X.sub.2                                                 (VIII)

wherein X₂ denotes lower alkoxy, unsubstituted or substituted phenoxy ora group of the formula, ##STR13## wherein R₇ and R₈ are as definedabove, or reacting any one of the monoazo naphthol compound of theformula (VII) or the compound of the formula (VIII) with cyanuricchloride or cyanuric fluoride, followed by the reaction with theremaining one, and then with the aromatic amine compound of the formula(III), to obtain a monoazo compound of the following formula (I"),##STR14## wherein R₁, R₂, R₃, R₄, R₅, A, B, X₂ and Z are as definedabove, which corresponds to the monoazo compound of the formula (I)having lower alkoxy, unsubstituted or substituted phenoxy or a group ofthe formula ##STR15## wherein R₇ and R₈ are as defined above.

The present invention also provides a process for dyeing or printingfiber materials, which comprises using the monoazo compound of theformula (I) or a salt thereof.

Among these monoazo compounds of the formula (I), preferred arecompounds of the following formulae, ##STR16## wherein R₅ is as definedabove, R₁₀ denotes hydrogen, methyl or ethyl, R₁₁ denotes hydrogen,chlorine or sulfo, R₁₂ denotes methyl, ethyl, acetyl or propionyl, R₁₃denotes hydrogen, methyl or ethyl, R₁₄ denotes hydrogen or sulfo, and Z₁denotes --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ OSO₃ H.

In the present invention, the lower alkyl group represented by R₁, R₂,R₃ and R₄ is intended to mean an alkyl group preferably having 1 to 4carbon atoms, and preferable substituents of the alkyl group includehydroxyl, cyano, C₁ -C₄ alkoxy, halogeno, carboxy, carbamoyl, cyano, C₁-C₄ alkoxycarbonyl, C₁ -C₁ -C₄ alkylcarbonyloxy, sulfo, sulfamoyl andthe like. Preferred examples of the unsubstituted or substitiuted alkylgroup represented by R₁, R₂, R₃ and R₄ are methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxyethyl,2-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl,3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl,cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl,2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl,2-bromethyl, 3chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl,carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl4-carbamoylmethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl,2-methoxycarbonylethyl, 2ehtoxycarbonylethyl, 3-methoxycarbonylpropyl,3-ethoxy-carbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonyl-butyl,methyocarbonyloxymethyl, ethylcarbonyloxymethyl,2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl,3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl,4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl,2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl,2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like. Ofthese, particularly preferred R₁, R₂ and R₄ are independently hydrogen,methyl or ethyl.

Examples of the acyl represented by R₃ are acetyl, propionyl, butyryl,isobutyryl, valeryl and benzoyl, and examples of the group, ##STR17##represented by R₃ are ##STR18## of these R₃, preferred are acetyl orpropionyl.

The phenylene group represented by A includes, for example, phenylenegroups unsubstituted and substituted with one or two members selectedfrom methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo, andthe napthylene group represented also by A includes naphthylene andsulfo-substituted naphthylene. Preferred examples of the phenylene andnaphthylene groups are as follows. ##STR19## (In the above formulae, theasterisked linkage is bonded to the group, ##STR20##

The symbol Y in the group, --SO₂ CH₂ CH₂ Y represented by Z, denotes agroup splittable by the action of an alkali, and includes, for example,sulfuric acid ester, thiosulfuric acid ester, phosphoric acid ester andacetic acid ester groups, and halogen atoms. Of these, particularlypreferred Z are --SO₂ CH═CH₂ and --SO₂ CH₂ CH₂ OSO₃ H.

Examples of the groups represented by B are as follows. ##STR21## (Inthe above formulae, the asterisked linkage is bonded to the group,##STR22##

With respect to the lower alkoxy group represented by X, preferred areones having 1 to 4 carbon atoms, which include for example, methoxy,ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy and the like.Particularly preferred are methoxy, ethoxy, n-propoxy, iso-propoxy andβ-ethoxyethoxy.

Preferred examples of the phenoxy group represented also by X are onesunsubstituted or substituted with one or two members selected from C₁-C₄ alkyl, C₁ -C₄ alkoxy, nitro, sulfo, carboxyl and chlorine.Particularly preferred are phenoxy, 3-or 4-sulfophenoxy, 2,4-or3,5-disulfophenoxy and the like.

With respect to the group, ##STR23## represented by X, preferred loweralkyl groups represented by R₇ and R₈ are ones which have 1 to 4 carbonatoms and are unsubstituted or substituted with one or two membersselected from C₁ -C₄ alkoxy, sulfo, carboxyl, hydroxy, chlorine, phenyland sulfate. Particularly preferred ones are methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxyethyl,2-sulfatoethyl, 2-suloethyl, 2-methoxyethyl and 2-carboxyethyl.

Preferred phenyl groups represented also by R₇ and R₈ are onesunsubstituted or substituted with one or two members selected from C₁-C₄ alkyl, C₁ -C₄ alkoxy, sulfo, carboxyl and chlorine. Of these,particularly preferred are phenyl, 2-, 3-or 4-sulfophenyl, 2-, 3-or4-carboxyphenyl, 3,4-, 3,5- or 3,6-disulfophenyl, and the like.

Preferred naphthyl groups represented also by X are ones unsubstitutedor substituted with one to three members selected from hydroxyl,carboxyl, sulfo, C₁ -C₄ alkyl, C₁ -C₄ alkoxy and chlorice. Of these,particularly preferred are 2-, 3-, 4-, 5-, 6-, 7-or 8-sulfo-2-naphthyl,1-, 5-, 6-, 7-or 8-sulfo-2-naphtyhl, 2,4-, 5,7-, 6,8-, 4,8-, 4,7-, 3,8-,4,6-, 3,7-or 3,6-disulfo-2naphthyl, 4,6,8-, 2,4,7-or3,6,8-trisulfo-1-naphthyl, 1,5,7-, 4,6,8-or 3,6,8-trisulfo-2-naphthyland the like.

Preferred benzyl groups represented also by R₇ and R₈ are onesunsubstituted or substituted with one or two members selected from C₁-C₄ alkyl, C₁ -C₄ alkoxy, sulfo and chlorine. Of these, particularlypreferred are benzyl and 2-, 3-or 4-sulfobenzyl.

The present monoazo compound of the above formula (I) may be in the formof a free acid or a salt of alkali or alkaline earth metal. Of these,preferred are sodium salt and potassium salt.

The monoazo compound of the above formula (I') having a chlorine orbromine atom as X in the formula (I) can be produced, for example, inthe following manner.

Any one of a diamine compound of the following formula (II), ##STR24##wherein R₂ and B are as defined above, or the aromatic amine of theformula (III) are subjected to first condensation with cyanuric chlorideor fluoride, followed by second condensation with the remaining one of(III) or (II). The first and second condensations can be carried out inan aqueous medium at a temperature of -10° to 50° C., preferably 0° to30° C., and at a pH of 1 to 10, preferably 2 to 7, and at a temperatureof 0° to 70° C. and at a preferred pH of 3 to 7, respectively.

The resulting amine compound represented by the formula (IV) can bediazotized at a temperature of -10° to 20° C. in a conventional manner,followed by coupling with the naphthol compound of the formula (V), at atemperature of -10° to 50° C., preferably 0° to 30° C., whilecontrolling the pH within a range of 1 to 7, preferably 1 to 5, wherebythe desired monoazo compound (I') can be produced.

Alternatively, the monoazo compound of the formula (I') can be producedalso in the following manner.

The diamine compound (II) or a nitro compound of the following formula(IX),

    H.sub.2 N - B - NO.sub.2

(IX)

wherein B is an defined above, is diazotized at a temperature of -10° to20° C. in a conventional manner, followed by coupling with the naphtholcompound (V) at a temperature of -10° to 50° C., preferably 0° to 30°C., while controlling the pH within a range of 1 to 7, preferably 1 to5. The resulting compound obtained using the nitro compound (IX) is thenfollowed with reduction at a temperature of 40° to 100° C. in thepresence of sodium sulfide. According to any one of the above manners,the monoazo naphthol compound of the formula (VII) can be produced.

Successively, any one of the manoazo naphthol compound (VII) or thearomatic amine compound (III) are subjected to first condensation withcyanuric chloride or fluoride, followed by second condensation with theremaining one of (III) or (VII), at a temperature of -10° to 50° C.,preferably 0° to 30° C., while controlling the pH within a range of 1 to10, preferably 2 to 7, and at a temperature of 0° to 70° C., preferably10° to 50° C., while controlling the pH within a range of 2 to 9,preferably 3 to 6, respectively, thereby obtaining the desired monoazocompound (I').

The monoazo compound of the formula (I") having as X in the formula (I)a lower alkoxy or unsubstituted or substituted phenoxy group or a groupof the formula, ##STR25## in which R₇ and R₈ are as defined above can beproduced, for example, in the following manner.

The monoazo compound (I") which can be produced in the manners asdescribed above is subjected to condensation with a compound representedby the following formula (VIII),

    H--X.sub.2                                                 (VIII)

wherein X₂ is as defined above, in an aqueous medium at a temperature of50° to 100° C., preferably 70° to 100° C., while controlling the pHwithin a range of 2 to 9, preferably 3 to 7.

Alternatively, any one of the monoazo naphthol compound (VII) or thecompound (VIII) is subjected to first condensation with cyanuricchloride or fluoride, followed by second condensation with the remainingone of (VIII) or (VII). The first condensation can be carried out at atemperature of -10° to 50° C., preferably 0° to 30° C., whilecontrolling the pH within a range of 1 to 10, preferably 4 to 7, and thesecond condensation at a temperature of 10° to 70° C., preferably 20° to50° C., while controlling the pH within a range of 2 to 10, preferably 4to 9. Successively, the resulting compound is subjected to condensationwith the aromatic amine compound (III) at a temperature of 50° to 100°C., preferably 80° to 100° C., while controlling the pH within a rangeof 2 to 9, preferably 3 to 7.

Thus, the desired monoazo compound of the formula (I") can be produced.

Particularly preferred examples of the naphthol compounds (V) usable forthe production of the monoazo compound (I) are as follows. ##STR26##

The compound (VIII) usable for the production of the monoazo compound(I) includes ammonia, aromatic and aliphatic amines, lower alcohols andsubstituted phenols.

Examples of the aromatic amine are 1-aminobenzene, 1-amino-2-, 3-or4-methylbenzene, 1-amino-2,4-, 2,5-, 3,4-or 3,5-dimethylbenzene,1-amino-2-, 3-or 4-ethylbenzene, 1-amino-2-, 3-or 4methoxybenzene,1-amino-4-ethoxbenzene, 1-amino-2-, 3-or 4-chloro-benzene, 3-or4-amino-phenymethanesulfonic acid, 2-, 3-or 4-aminobenzenesulfonic acid,3-methylamino-benzenesulfonic acid, 3-methylamino-benzenesulfonic acid,4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid,5-aminobenzene-1,3-disulfonic acid, 2-aminobenezene-1,4-disulfonic acid,4-aminobenzene-1,3- disulfonic acid, 2-, 3-or 4-aminobenzoic acid,5-aminobenzene-1,3-dicarboxylic acid, 5amino-2-hydroxybenzenesulfonicacid, 4-amino-2-hydroxybenzenesulfonic acid,5-amino-2-ethoxybenzene-sulfonic acid, N-methylaminobenzene,N-ethylaminobenzene, 1-ethylamino-3-or 4-methylbenzene,1-ethylamino-4-chlorobenzene, 1-ethylamino-3-or 4-methylbenzene,1-(2-hydroxyethyl)amino-3-methylbenzene, 3-or 4-methylaminobenzoic acid,3-or 4-methylaminobenzenesulfonic acid, 2-aminonaphthalene-1-sulfonicacid, 4-aminonaphtalene-1-sulfonic acid, 5-aminonaphthalene-1sulfonicacid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1sulfonicacid, 8-aminonaphthalene-1-sulfonic acid, 1-aminonapthalene-2-sulfonicacid, 4-aminonapthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonicacid, 6-aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonicacid, 7-methylaminonaphthalene-2sulfonic acid,7-ethylaminonaphthalene-2-sulfonic acid,7-butylaminonaphthalene-2sulfonic acid,7-isobutyl-aminonaphthalene-2-sulfonic acid,8-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-1,3-disulfonicacid, 5-aminonaphthalene-1,3-disulfonic acid,6-aminonaphthalene-1,3-disulfonic acid,7-aminonaphthalene-1,3-disulfonic aicd,8-aminonaphthalene-1,3-disulfonic acid,2-aminonaphthalene-1,5-disulfonic acid,3-aminonaphthalene-1,5-disulfonic acid, 4aminonaphthalene-1,5-disulfonicacid, 4-aminonaphthalene-1,6-disulfonic acid,8-aminonaphthalene-1,6-disulfonic acid,4-aminonaphthalene-1,7-disulfonic acid,3-aminonaphthalene-2,6-disulfonic acid,4-aminonaphthalene-2,6-disulfonic acid,3-aminonaphthalene-2,7-disulfonic acid,4-aminonaphthalene-2,7-disulfonic acid,6-aminonaphthalene-1,3,5-trisulfonic acid,7-aminonaphthalene-1,3,5-trisulfonic acid,4-aminonaphthalene-1,3,6-trisulfonic acid,7-aminonaphthalene-1,3,6-trisulfonic acid,8-aminonaphthalene-1,3,6-trisulfonic acid,4-aminonaphthalene-1,3,7-trisulfonic acid and the like.

Examples of the aliphatic amines are methylamine, ethylamine,n-propylamine, iso-propylamine, n-butylamine, iso-butylamine,sec-butylamine, dimethylamine, diethylamine, methylethylamine,allylamine, 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol,2-methylaminoethanol, bis-(2-hydroxyethyl-amine,2-acetylaminoethylamine, 1-amino-2-propanol, 3-methoxypropylamine,1-amino-3-dimethylaminopropane, 2aminoethanesulfonic acid,aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid,3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid,methylaminoacetic acid, ε-aminocaproic acid, benzylamine, 2-, 3- or4-chlorobenzylamine, 4-methylbenzylamine, N-methylbenzylamine, 2-, 3- or4-sulfobenzylamine, 2phenylethylamine, 1-phenylethylamine,1-phenyl-2-propylamine and the like.

Examples of the lower alcohols are methanol, ethanol, n-propanol,iso-propanol, n-butanol, iso-butanol and the like.

Examples of the substituted phenols are 3- or 4-sulfophenol, 2,4- or3,5-disulfophenol, 2-nitro-4-sulfophenol, 2-chloro-4-sulfophenol and thelike.

Of these compounds exemplified for the compound of the formula (VIII),particularly preferred are, for example, aniline, N-methylaminobenzene,N-ethylaminobenzene, 3-aminobenzenesulfonic acid,3-methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid,4-aminobenzenesulfonic acid, 4-methylaminobenzene sulfonic acid,4-ethylaminobenzenesulfonic acid, mono- or di-ethanolamine and the like.

Examples of the nitro compound (XI) are as follows: ##STR27##

The monoazo compound (I) in accordance with the present invention isfiber-reactive and useful for dyeing or printing hydroxylgroup-containing and amide group-containing materials. The materials arefavorably in a fibrous form including unmixed or mixed fiber spinning.

The hydroxyl group-containing materials include natural or synthetichydroxyl group-containing materials such as cellulose fiber materials,cellulose-containing fiber materials, regenerated products thereof andpolyvinyl alcohol. Examples of the cellulose fiber materials are cottonand other vegetable fibers such as linen, hemp, jute and ramie fibers.Examples of the regenerated cellulose fibers are viscose staple andfilament viscose. Examples of the cellulose-containing fiber materialsare mixed fiber materials such as cellulose/polyester, cellulose/wook,cellulose/acryl and the like.

The amide group-containing materials, include sythethic or naturalpolyamide and polyurethane. Examples of the materials, particularly inthe fibrous forms, are wool and other animal furs, silk, leather,polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The dyeing may be carried out in a suitable manner, which can beselected from conventional manners depending on the physical andchemical properties of said fiber materials.

For example, cellulose fiber materials can be dyed using the presentcompound by an exhaustion dyeing, padding including cold batch-up dyeingor printing method.

The exhaustion dyeing can be carried out at a relatively low temperaturein the presence of an acid binding agent such as sodium carbonate,trisodium phosphate, sodium hydroxide and the like, if desired using aneutral salt such as sodium sulfate, sodium chloride and the like,optionally together with dissolving assistants, penetrants or leveldyeing agents. The neutral salt which can be used for promotingexhaustion of the dye may be added to a dye bath at the time when a bathtemperature reaches a level desired for the dyeing, or prior thereto.Alternatively, the neutral salt may be added thereto dividedly.

The padding can be carried out by padding the fiber materials at ambienttemperature or an elevated temperature, and after drying, steaming ordry-heating the material to perform the dye-fixation.

The printing can be carried out in a one-phase or two-phase manner. Theone-phase printing may be conducted by printing the fiber materials witha printing paste containing an acid binding agent such as sodium hyrogencarbonate and the like, followed by steaming at a temperature of 100° to160° C. The two-phase printing may be conducted by printing the fibermaterials with a neutral or weakly acidic printing paste, and passingthe materials through a hot alkaline bath containing an electrolyte orover-padding the materials with an alkaline padding liquor containing anelectrolyte, followed by a steaming or dry-heating treatment.

For the preparation of the printing paste, a paste or emulsifier such assodium alginate, starch ether and the like may be used, if desired,together with a conventional auxiliary agent such as urea and/or adispersing agent.

The acid binding agent useful for fixing the compound of the presentinvention on the cellulose fiber materials includes water-soluble basicsalts consisting of alkali or alkaline earth metals and inorganic ororganic acids or compounds capable of liberating alkalis under heatingconditions. Preferred are alkali metal hydroxides and alkali metal saltsof inorganic or organic acids having a weak or medium strength.Particularly preferred are sodium salts and potassium salts. Examplesthereof are sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, sodium formate, potassium carbonate, sodiumdihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate,sodium silicate, sodium trichloroacetate and the like.

The dyeing of natural or synthetic polyamide and polyurethane fibermaterials can be carried out by performing exhausting in an acid or weakacid bath, while controlling the pH value, and then making the bathneutral, or in some cases alkaline to perform the fixation. The dyeingtemperature ranges usually from 60° to 120° C. In order to achive alevel dyeing, there may be used a conventional level dyeing agent suchas a condensation product between cyanuric chloride and 3 times by moleof aminobenzene-sulfonic acid or aminonapthalenesulfonic acid, or anaddition product between stearylamine and ethylene oxide, and the like.

The present monoazo compound (I) can be characterized by excellent dyeperformances in the dyeing and printing of fiber materials, particularlycellulose fiber materials. For example, the compound can give a dyedproduct excellent in light fastness, perspiration-light fastness,perspiration fastness, washing fastness, peroxide-washing fastness,chlorine fastness, chlorine bleaching fastness, acid-hydrolysisfastness, alkali fastness, abrasion fastness and iron fastness,particularly formalin fastness and formalin-light fastness. The monoazocompound (I) can also exhibit excellent build-up, level-dyeing andwash-off properties and high solubility as well as high exhaustion andfixation percentages. Moreover, the monoazo compound (I) can hardly beaffected by changes in a dyeing temperature, a kind of alkali agents, anamount to be used of inorganic salts and dyeing bath ratio, so that adyes product with a constant quality can be obtained with superiorreproducibility. Furthermore, in the cold batch-up dyeing method, themonoazo compound (I) can exhibit characteristic features such that abuild-up property and alkali stability including insusceptibility tohydrolysis by the alkali agents are excellent, and no difference indyeing depth and color shade of dyed products can be observed in bothcases where the fixing procedures are carried out at a relatively lowtemperature and at 25° C., respectively.

The present invention is illustrated in more detail with reference tothe following Examples, which are only illustrative, but not limitative.In Examples, parts and % are by weight.

EXAMPLE 1

2,4-diaminobenzenesulfonic acid (18.8 parts) was added to a suspensionprepared by dispersing cyanuric chloride (18.5 parts) in ice water (250parts), and the mixture was stirred for 6 hours at 0° to 5° C., whilecontrolling the pH within a range of 2 to 4 using a 20% aqueous solutionof sodium carbonate, thereby performing a first condensation.

Into the resulting reaction mixture was added1-aminobenzene-3-β-sulfatoethylsulfone (28.1 parts), and the mixture wasstirred for 7 hours at 10° to 20° C., while controlling the pH within arange of 4 to 6 using a 20% aqueous solution of sodium carbonate,thereby performing a second condensation.

Successively, concentrated hydrochloric acid (25.3 parts) was added tothe reaction mixture, and then a 35% aqueous solution of sodium nitrite(21.7 parts) was added thereto, thereby performing a diazotization.After an excess nitrous acid had been decomposed,7-methylamino-1-naphthol-3-sulfonic acid (25.3 parts) was added, and theresulting mixture was stirred over night at 0° to 5° C., whilecontrolling the pH within a range of 1 to 3 using a 20% aqueous solutionof sodium carbonate, thereby performing a coupling reaction. Thereafter,the reaction mixture was heated to 40° C., adjusted to pH 4 to 6 andthen subjected to salting out using sodium chloride (20 parts). Thecrystals produced were separated on a filter, washed and then dried at60° C., thereby obtaining a monoazo compound represented by thefollowing formula (1) in a free acid form. ##STR28##

EXAMPLES 2 to 62

Example 1 was repeated, provided that each naphthol compound of theformula (V) shown in a second column in the following table was used inplace of 7-methylamino-1-naphthol-3-sulfonic acid, and each diaminecompound of the formula (II) shown in a third column in place of2,4-diaminobenzenesulfonic acid, cyanuric chloric or cyanuric fluorideas shown in a fourth column in which Cl and F denote cyanuric chlorideand cyanuric fluoride, respectively, and each aromatic amine compound ofthe formula (III) shown in a fifth column in place of1-aminobenzene-3β-sulfatoethylsulfone, thereby obtaining eachcorresponding desired monoazo compound. The compound of the formula,##STR29## which was used in Examples 23 and 34, was prepared byacetylating the amino groups of 2,4-diaminobenzenesulfonic acid,followed by chlorination and hydrolysis.

    __________________________________________________________________________    Ex-                               Cyanuric                                    am-                               chloride                                    ple                                                                              Compound of         Compound of                                                                              or   Compound of                            No.                                                                              Formula (V)         Formula (II)                                                                             fluoride                                                                           Formula (III)       Shade              __________________________________________________________________________     2                                                                                ##STR30##                                                                                         ##STR31## Cl                                                                                  ##STR32##          Bluish red          3 "                   "          "                                                                                   ##STR33##          Bluish red          4 "                   "          "                                                                                   ##STR34##          Bluish red          5 "                                                                                                  ##STR35## "                                                                                   ##STR36##          Bluish red          6 "                   "          "                                                                                   ##STR37##          Bluish red          7 "                   "          F                                                                                   ##STR38##          Bluish red          8 "                                                                                                  ##STR39## Cl                                                                                  ##STR40##          Bluish red          9 "                   "          "                                                                                   ##STR41##          Bluish red         10 "                                                                                                  ##STR42## "                                                                                   ##STR43##          Bluish red         11 "                   "          "                                                                                   ##STR44##          Bluish red         12 "                   "          F                                                                                   ##STR45##          Bluish red         13 "                                                                                                  ##STR46## "                                                                                   ##STR47##          Bluish red         14 "                   "          Cl                                                                                  ##STR48##          Bluish red         15 "                                                                                                  ##STR49## "    "                   Bluish red         16                                                                                ##STR50##                                                                                         ##STR51## "                                                                                   ##STR52##          Bluish red         17 "                   "          F                                                                                   ##STR53##          Bluish red         18 "                                                                                                  ##STR54## Cl                                                                                  ##STR55##          Bluish red         19 "                                                                                                  ##STR56## "                                                                                   ##STR57##          Bluish red         20 "                   "          "                                                                                   ##STR58##          Bluish red         21 "                                                                                                  ##STR59## "    "                   Bluish red         22                                                                                ##STR60##                                                                                         ##STR61## "                                                                                   ##STR62##          Bluish red         23 "                                                                                                  ##STR63## "                                                                                   ##STR64##          Bluish red         24 "                                                                                                  ##STR65## "    "                   Bluish red         25                                                                                ##STR66##                                                                                         ##STR67## F                                                                                   ##STR68##          Bluish red         26 "                                                                                                  ##STR69## Cl                                                                                  ##STR70##          Bluish red         27 "                                                                                                  ##STR71## "    "                   Bluish red         28                                                                                ##STR72##                                                                                         ##STR73## F                                                                                   ##STR74##          Bluish red         29 "                                                                                                  ##STR75## " 41 Bluish red                             30                                                                                ##STR76##                                                                                         ##STR77## Cl                                                                                  ##STR78##          Bluish red         31 "                                                                                                  ##STR79## "    "                   Red                32 "                   "          "                                                                                   ##STR80##          Red                33 "                                                                                                  ##STR81## "                                                                                   ##STR82##          Bluish red         34 "                                                                                                  ##STR83## "                                                                                   ##STR84##          Bluish red         35 "                                                                                                  ##STR85## "    "                   Red                36 "                   "          F                                                                                   ##STR86##          Red                37 "                                                                                                  ##STR87## "    "                   Red                38 "                   "          Cl                                                                                  ##STR88##          Red                39                                                                                ##STR89##                                                                                         ##STR90## "                                                                                   ##STR91##          Red                40 "                   "          "                                                                                   ##STR92##          Red                41 "                                                                                                  ##STR93## "    "                   Bluish red         42 "                   "          "                                                                                   ##STR94##          Bluish red         43 "                                                                                                  ##STR95## "    "                   Red                44 "                   "          "                                                                                   ##STR96##          Red                45 "                                                                                                  ##STR97## F                                                                                   ##STR98##          Bluish red         46 "                   "          Cl                                                                                  ##STR99##          Bluish red         47 "                                                                                                  ##STR100##                                                                              "    "                   Red                48                                                                                ##STR101##         "          F                                                                                   ##STR102##         Red                49 "                                                                                                  ##STR103##                                                                              Cl                                                                                  ##STR104##         Red                50 "                                                                                                  ##STR105##                                                                              "                                                                                   ##STR106##         Red                51                                                                                ##STR107##                                                                                        ##STR108##                                                                              "                                                                                   ##STR109##         Red                52 "                   "          "                                                                                   ##STR110##         Red                53 "                                                                                                  ##STR111##                                                                              "    "                   Bluish red         54 "                   "          "                                                                                   ##STR112##         Bluish red         55 "                                                                                                  ##STR113##                                                                              "    "                   Red                56 "                   "          "                                                                                   ##STR114##         Red                57 "                                                                                                  ##STR115##                                                                              F                                                                                   ##STR116##         Bluish red         58 "                                                                                                  ##STR117##                                                                              Cl   "                   Red                59 "                   "          "                                                                                   ##STR118##         Red                60 "                                                                                                  ##STR119##                                                                              "    "                   Red                61                                                                                ##STR120##                                                                                        ##STR121##                                                                              "                                                                                   ##STR122##         Red                62 "                                                                                                  ##STR123##                                                                              "    "                   Red                __________________________________________________________________________

EXAMPLE 63

A solution containing 2-methoxy-4-nitroaniline-5-sulfonic acid (24.8parts) and a 35% aqueous solution of sodium nitrite (21.7 parts) inwater (150 parts) was introduced into a solution containing ice water(300 parts) and concentrated hydrochloric acid (35.5 parts), whilecontrolling the temperature to 0° to 5° C. ,and the mixture was stirredfor 1 hour at this temperature to perform a diazotization.

Successively, after an excess nitrous acid had been decomposed,7-ethylamino-1-naphthol-3-sulfonic acid (26.7 parts) was added to thereaction mixture, and the mixture was stirred for 2 hours at 0° to 5°C., while controlling the pH within a range of 1 to 3 using a 20%aqueous solution of sodium carbonate, thereby performing a couplingreaction. Thereafter, the reaction mixture was adjusted to pH 8 to 10,and mixed with sodium sulfide (10.7 parts), and the mixture was heatedto 60° C. and stirred for 3 hours at this temperature to perform areduction. Then, the reaction mixture was mixed with sodium cholride (40parts) to deposit crystals, which were collected on a filter and washed.The resulting wet cake was dissolved in water (400 parts). The solutionwas mixed with cyanuric chloride (16.7 parts), and the mixture wasstirred for 5 hours at 0° to 10° C., while controlling the pH within arange of 2 to 3 using a 20% aqueous solution of sodium carbonate,thereby performing a first condensation. To this reaction mixture wasadded 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (37parts), and the mixture was stirred for 15 at 20° to 30° C., whilecontrolling the pH within a range of 4 to 5 using a 20% aqueous solutionof sodium carbonate, thereby performing a second condensation.Thereafter, the reaction mixture was mixed with sodium chloride (40parts) to deposit crystals, which were collected on a filter, washed anddried at 60° C. to obtain a desired monoazo compound represented by thefollowing formula (63) in a free acid form. ##STR124##

EXAMPLES 64 to 86

Example 63 was repeated, provided that each naphtol compound of theformula (V) shown in a second column of the following table was used inplace of 7-ethylamino-1-naphthol-3-sulfonic acid, and each compound ofthe formula (IX) shown in a third column in place of2-methoxy-4-nitroaniline-5-sulfonic acid, cyanuric chloride or cyanuricfluoride as shown in a fourth column in which Cl and F denote cyanuricchloride and cyanuric fluoride, respectively, and each aromatic aminecompound of the formula (III) shown in a fifth column in place of2-aminonaphthalene-6-β-sulfatoethyl -sulfone-1-sulfonic acid, therebyobtaining the desired corresponding monoazo compound.

    __________________________________________________________________________                                      Cyanuric                                                                      chloride                                    Example                                                                            Compound of        Compound of                                                                             or   Compound of                            No.  Formula (V)        Formula (IX)                                                                            fluoride                                                                           Formula (III)       Shade              __________________________________________________________________________    64                                                                                  ##STR125##                                                                                       ##STR126##                                                                             Cl                                                                                  ##STR127##         Bluish red         65                                                                                  ##STR128##                                                                                       ##STR129##                                                                             Cl                                                                                  ##STR130##          Bluish red        66                                                                                  ##STR131##                                                                                       ##STR132##                                                                             Cl                                                                                  ##STR133##         Bluish red         67                                                                                  ##STR134##                                                                                       ##STR135##                                                                             Cl                                                                                  ##STR136##         Bluish red         68                                                                                  ##STR137##                                                                                       ##STR138##                                                                             Cl                                                                                  ##STR139##         Bluish red         69                                                                                  ##STR140##                                                                                       ##STR141##                                                                             F                                                                                   ##STR142##         Bluish red         70                                                                                  ##STR143##                                                                                       ##STR144##                                                                             Cl                                                                                  ##STR145##         Bluish red         71                                                                                  ##STR146##                                                                                       ##STR147##                                                                             Cl                                                                                  ##STR148##         Bluish red         72                                                                                  ##STR149##                                                                                       ##STR150##                                                                             Cl                                                                                  ##STR151##         Bluish red         73                                                                                  ##STR152##                                                                                       ##STR153##                                                                             F                                                                                   ##STR154##         Bluish red         74                                                                                  ##STR155##                                                                                       ##STR156##                                                                             F                                                                                   ##STR157##         Bluish red         75                                                                                  ##STR158##                                                                                       ##STR159##                                                                             Cl                                                                                  ##STR160##         Bluish red         76                                                                                  ##STR161##                                                                                       ##STR162##                                                                             Cl                                                                                  ##STR163##         Bluish red         77                                                                                  ##STR164##                                                                                       ##STR165##                                                                             Cl                                                                                  ##STR166##         Bluish red         78                                                                                  ##STR167##                                                                                       ##STR168##                                                                             Cl                                                                                  ##STR169##         Bluish red         79                                                                                  ##STR170##                                                                                       ##STR171##                                                                             Cl                                                                                  ##STR172##         Bluish red         80                                                                                  ##STR173##                                                                                       ##STR174##                                                                             Cl                                                                                  ##STR175##         Bluish red         81                                                                                  ##STR176##                                                                                       ##STR177##                                                                             Cl                                                                                  ##STR178##         Bluish red         82                                                                                  ##STR179##                                                                                       ##STR180##                                                                             Cl                                                                                  ##STR181##         Bluish red         83                                                                                  ##STR182##                                                                                       ##STR183##                                                                             F                                                                                   ##STR184##          Bluish red        84                                                                                  ##STR185##                                                                                       ##STR186##                                                                             F                                                                                   ##STR187##         Bluish red         85                                                                                  ##STR188##                                                                                       ##STR189##                                                                             Cl                                                                                  ##STR190##         Bluish red         86                                                                                  ##STR191##                                                                                       ##STR192##                                                                             Cl                                                                                  ##STR193##         Bluish             __________________________________________________________________________                                                               red            

EXAMPLE 87

The monoazo compound (98.7 parts) represented by the following formulain free acid form, ##STR194## which had been obtained in Example 2, wasdissolved in water (500 parts), and to this solution was added3-aminobenzenesulfonic acid (34.6 parts). The mixture was heated up to80° to 85° C., while controlling the pH within a range of 4 to 6 using a20% aqueous sodium carbonate solution, and then stirred for 7 hours atthat temperature and that pH. Thereafter, the reaction mixture was mixedwith sodium chloride (45 parts) to deposit crystals, which werecollected on a filter, washed and dried at 60° C. to obtain a monoazocompound of the following formula (87) in a free acid form. ##STR195##

EXAMPLE 88 to 119

Example 87 was repeated, provided that each monoazo compound shown belowwas used in place of the monoazo compound obtained in Example 2, themonoazo compound used being shown in a second column of the followingtable (in which the monoazo compound used is expressed in terms of eachExample No.), and each compound of the formula (VIII) in place of3-amino -benzenesulfonic acid, thereby obtaining the correspondingdesired monoazo compound.

    ______________________________________                                               Example No.                                                                   of Monoazo                                                             Example                                                                              compound   Compound of                                                 No.    obtained   Formula (VIII)     Shade                                    ______________________________________                                         88     1                                                                                        ##STR196##        Bluish red                                89     4                                                                                        ##STR197##        Bluish red                                90     5         NH(CH.sub.2 CH.sub.2 OH).sub.2                                                                   Bluish                                                                        red                                       91     8                                                                                        ##STR198##        Bluish red                                92    10                                                                                        ##STR199##        Bluish red                                93    14                                                                                        ##STR200##        Bluish red                                94    16                                                                                        ##STR201##        Bluish red                                95    20                                                                                        ##STR202##        Bluish red                               96     21                                                                                        ##STR203##        Bluish red                                97    22                                                                                        ##STR204##        Bluish red                                98    24                                                                                        ##STR205##        Bluish red                                99    27                                                                                        ##STR206##        Bluish red                               100    28                                                                                        ##STR207##        Bluish red                               101    30                                                                                        ##STR208##        Bluish red                               102    31                                                                                        ##STR209##        Red                                      103    35         NH.sub.2 (CH.sub.2 CH.sub.2 OH)                                                                  Red                                      104    40                                                                                        ##STR210##        Red                                      105    41                                                                                        ##STR211##        Bluish red                               106    44                                                                                        ##STR212##        Red                                      107    47                                                                                        ##STR213##        Red                                      108    63         H.sub.2 NCH.sub.3  Bluish                                                                        red                                      109    84                                                                                        ##STR214##        Bluish red                               110    66                                                                                        ##STR215##        Bluish red                               111    69                                                                                        ##STR216##        Bluish red                               112    71         H.sub.2 NCH.sub.2 CH.sub.2 OSO.sub.3 H                                                           Bluish                                                                        red                                      113    72         H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.3                                                             Bluish                                                                        red                                      114    77                                                                                        ##STR217##        Bluish red                               115    80                                                                                        ##STR218##        Bluish red                               116    82                                                                                        ##STR219##        Bluish red                               117    83                                                                                        ##STR220##        Bluish red                               118    84                                                                                        ##STR221##        Bluish red                               119    86                                                                                        ##STR222##        Bluish red                               ______________________________________                                    

EXAMPLE 120

A 35% aqueous solution of sodium nitrite (21.7 parts) was added to asolution containing 2-amino -5-aminomethylnaphthalene-1-sulfonic acid(27.4 parts) and concentrated hydrochloric acid (35.5 parts) in icewater (300 parts), while controlling the temperature within a range of0° to 5° C., and the mixture was stirred for 1 hour at that temperatureto perform a diazotization. Successively after an excess nitrous acidhad been decomposed, 7-ethylamino-1-naphthol-3-sulfonic acid (26.7parts) was added thereto, and the mixture was stirred for 12 hours at 0°to 5° C., while controlling the pH within a range of 3 to 5 using a 20%aqueous solution of sodium carbonate, thereby performing a couplingreaction to obtain a monoazo compound-containing solution.

On the other hand, water (30 parts) and sodium carbonate (8.4 parts)were added to methanol (300 parts), and cyanuric chloride (18.5 parts)was further added thereto. The mixture was stirred for 30 minutes at 0°to 10° C. The resulting reaction mixture was added to the above monoazocompound-containing solution, and the mixture was stirred for 6 hours at30° to 40° C., while controlling the pH within a range of 7 to 8 using a20% aqueous solution of sodium carbonate.

Moreover, 1-ethylaminobenzene-4-β-sulfatoethyl -sulfone (30.9 parts) wasadded to the above reaction mixture, and the resulting mixture washeated upto 80° 90° C., while controlling the pH within a range of 3 to5 using a 20% aqueous solution of sodium carbonate, and then stirred for15 hours at that temperature and that pH. Thereafter, the reactionmixture was cooled to 40° C. and mixed with sodium chloride (40 parts)to deposit crystals, which were collected on a filter, washed and driedat 60° C. to obtain a monoazo compound of the following formula (120) ina free acid form. ##STR223##

EXAMPLES 121 to 141

Example 120 was repeated, provide that each diamine compound of theformula (II) shown in a third colunm of the following table was used inplace of 2-amino-5-aminomethylnaphthalene-1-sulfonic acid, each naphtholcompound of the formula (V) shown in a second column in place of7-ethylamino-1-naphthol-3-sulfonic acid, each compound of the formula(VIII) shown in fourth column in place of methanol, and each aromaticamine compound of the formula (III) shown in a fifth column in place of1-ethylaminobenzene-4-β-sulfatoethylsulfone, thereby obtaining thecorresponding desired monoazo compound.

    __________________________________________________________________________    Ex-                                                                           am-                            Compound of                                    ple                                                                              Compound of     Compound of Formula  Compound of                           No.                                                                              Formula (V)     Formula (II)                                                                              (VIII)   Formula (III)      Shade              __________________________________________________________________________    121                                                                               ##STR224##                                                                                    ##STR225## C.sub.2 H.sub.5 OH                                                                      ##STR226##        Bluish red         122                                                                               ##STR227##                                                                                    ##STR228## C.sub.2 H.sub.5 OH                                                                      ##STR229##        Bluish red         123                                                                               ##STR230##                                                                                    ##STR231## CH.sub.3 CH.sub.2 CH.sub.2 OH                                                           ##STR232##        Bluish red         124                                                                               ##STR233##                                                                                    ##STR234## CH.sub.3 OH                                                                             ##STR235##        Red                125                                                                               ##STR236##                                                                                    ##STR237## CH.sub.3 OH                                                                             ##STR238##        Red                126                                                                               ##STR239##                                                                                    ##STR240## CH.sub.3 OH                                                                             ##STR241##        Yel- lowish                                                                   red                127                                                                               ##STR242##                                                                                    ##STR243## CH.sub. 3 OH                                                                            ##STR244##        Yel- lowish                                                                   red                128                                                                               ##STR245##                                                                                    ##STR246## C.sub.2 H.sub.5 OH                                                                      ##STR247##        Red                129                                                                               ##STR248##                                                                                    ##STR249## CH.sub.3 OH                                                                             ##STR250##        Red                130                                                                               ##STR251##                                                                                    ##STR252## CH.sub.3 CH.sub.2 CH.sub.2 OH                                                           ##STR253##        Yel- lowish                                                                   red                131                                                                               ##STR254##                                                                                    ##STR255## CH.sub.3 OH                                                                             ##STR256##        Yel- lowish                                                                   red                132                                                                               ##STR257##                                                                                    ##STR258## CH.sub.3 OH                                                                             ##STR259##        Red                133                                                                               ##STR260##                                                                                    ##STR261## CH.sub.3 OH                                                                             ##STR262##        Red                134                                                                               ##STR263##                                                                                    ##STR264## CH.sub.3 OH                                                                             ##STR265##        Yel- lowish                                                                   red                135                                                                               ##STR266##                                                                                    ##STR267## C.sub.2 H.sub.5 OH                                                                      ##STR268##        Yel- lowish                                                                   red                136                                                                               ##STR269##                                                                                    ##STR270## CH.sub.3 OH                                                                             ##STR271##        Yel- lowish                                                                   red                137                                                                               ##STR272##                                                                                    ##STR273## CH.sub.3 OH                                                                             ##STR274##        Yel- lowish                                                                   red                138                                                                               ##STR275##                                                                                    ##STR276## CH.sub.3 OH                                                                             ##STR277##        Red                139                                                                               ##STR278##                                                                                    ##STR279## CH.sub.3 OH                                                                             ##STR280##        Bluish red         140                                                                               ##STR281##                                                                                    ##STR282##                                                                                ##STR283##                                                                             ##STR284##        Bluish red         141                                                                               ##STR285##                                                                                    ##STR286## C.sub.2 H.sub.5 OH                                                                      ##STR287##        Bluish             __________________________________________________________________________                                                               red            

EXAMPLE 142

Example 1 was repeated, provided that2-methyl-amino-8-hydroxynaphtalene-3,6-disulfonic acid (33.3 parts) wasused in placed of 7-methylamino-1-naphthol-3-sulfonic acid (25.3 parts),thereby obtaining a desired monoazo compound of the following formula(142) in a free acid form. ##STR288##

EXAMPLES 143 to 196

Example 1 was repeated, provided that each naphthol compound of theformula (V) shown in a second column of the following table was used inplace of 7-methylamino-1-naphthol-3-sulfonic acid, each diamine compoundof the formula (II) shown in a third column in place of 1,3-diaminobenzene-4-sulfonic acid, cyanuric chloride or cyanuric fluorideas shown in a fourth column in which Cl and F denote cyanuric chlorideand cyanuric fluoride, respectively, and each aromatic amine compound ofthe formula (III) shown in a fifth column in place of1-aminobenzene-3-β-sulfatoethylsulfone, thereby obtaining thecorresponding desired monoazo compounds.

      Example Compound of Compound of Cyanuric Compound of  No. Formula (V)     Formula (II) chloride or fluoride Formula (III) Shade             143      ##STR289##      ##STR290##      Cl      ##STR291##      Red      144 " " "     ##STR292##      "      145 "     ##STR293##      F      ##STR294##      "      146 "     ##STR295##      "      ##STR296##      Bluish red      147     ##STR297##      ##STR298##      Cl      ##STR299##      Bluish red      148 " " "     ##STR300##      "      149 "     ##STR301##      "      ##STR302##      Red      150 " " F     ##STR303##      "      151     ##STR304##      ##STR305##      " " "      152     ##STR306##      ##STR307##      Cl      ##STR308##      Red      153 "     ##STR309##      " " Bluish red      154 " " "     ##STR310##      "      155     ##STR311##      ##STR312##      "      ##STR313##      Red      156 " " "     ##STR314##      "      157     ##STR315##      ##STR316##      Cl      ##STR317##      Bluish red      158 " " "     ##STR318##      "      159 "     ##STR319##      " " "      160 " " "     ##STR320##      "      161 "     ##STR321##      "      ##STR322##      Red      162     ##STR323##      ##STR324##      Cl      ##STR325##      Red      163 "     ##STR326##      " " "      164 " " F     ##STR327##      "      165 "     ##STR328##      " " Bluish red      166 " " Cl     ##STR329##      "      167     ##STR330##      ##STR331##      Cl      ##STR332##      Red      168 " " "     ##STR333##      "      169 "     ##STR334##      " " Bluish red      170 " " "     ##STR335##      "      171 "     ##STR336##      " " "       172     ##STR337##      ##STR338##      F      ##STR339##      Bluish red      173 "     ##STR340##      Cl      ##STR341##      Red      174 " " "     ##STR342##      "      175 "     ##STR343##      " "  Bluish red      176 " " "     ##STR344##      "      177     ##STR345##      ##STR346##      Cl      ##STR347##      Red      178 " " "     ##STR348##      "      179     ##STR349##      ##STR350##      "      ##STR351##      "      180 "     ##STR352##      "      ##STR353##      Bluish red      181 "     ##STR354##      F      ##STR355##      "      182     ##STR356##      ##STR357##      Cl      ##STR358##      Red      183 "     ##STR359##      "      ##STR360##      "      184 "     ##STR361##      F      ##STR362##      Bluish red      185     ##STR363##      ##STR364##      Cl      ##STR365##      Red      186 " " "     ##STR366##      "      187     ##STR367##      ##STR368##      Cl      ##STR369##      Red      188 "     ##STR370##      " " "      189 " " "     ##STR371##      "      190 "     ##STR372##      " " "      191     ##STR373##      ##STR374##      "      ##STR375##      "      192     ##STR376##      ##STR377##      Cl      ##STR378##      Red      193 "     ##STR379##       " " Bluish red      194 "     ##STR380##      " " Red      195     ##STR381##      ##STR382##      "      ##STR383##      "      196 "     ##STR384##      " " "

EXAMPLE 197

Example 63 was repeated, provided that2-methyl-amino-8-hydroxynaphthalene-3, 6-disulfonic acid (33.3 parts)was used in place of 7-ethylamino-1-naphthol-3-sulfonic acid (26.7parts), thereby obtaining a monoazo compound represented by thefollowing formula (197) in a free acid form. ##STR385##

EXAMPLES 198 to 233

Example 63 was repeated, provided that each naphthol compound of theformula (V) shown is a second column of the following table was used inplace of 7-ethylamino- 1-naphthol-3-sulfonic acid, each nitro compoundof the formula (IX) shown in a third column in place of2-methoxy-4-nitroaniline-5-sulfonic acid, cyanuric chloride or fluorideas shown in a fourth column in which Cl and F denote cyanuric chlorideand cyanuric fluoride, respectively, and each aromatic amine compoundshown in a fifth column in place of2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid, therebyobtaining the corresponding desired monoazo compound.

    __________________________________________________________________________    Ex-                               Cyanuric                                    am-                               chloride                                    ple                     Compound of                                                                             or                                          No.                                                                              Compound of Formula (V)                                                                            Formula (IX)                                                                            fluoride                                                                           Compound of Formula                                                                               Shade              __________________________________________________________________________    198                                                                               ##STR386##                                                                                         ##STR387##                                                                             Cl                                                                                  ##STR388##         Bluish red         199                                                                               ##STR389##                                                                                         ##STR390##                                                                             Cl                                                                                  ##STR391##         Bluish red         200                                                                               ##STR392##                                                                                         ##STR393##                                                                             Cl                                                                                  ##STR394##         Bluish red         201                                                                               ##STR395##                                                                                         ##STR396##                                                                             Cl                                                                                  ##STR397##         Bluish red         202                                                                               ##STR398##                                                                                         ##STR399##                                                                             F                                                                                   ##STR400##         Bluish red         203                                                                               ##STR401##                                                                                         ##STR402##                                                                             Cl                                                                                  ##STR403##         Bluish red         204                                                                               ##STR404##                                                                                         ##STR405##                                                                             Cl                                                                                  ##STR406##         Bluish red         205                                                                               ##STR407##                                                                                         ##STR408##                                                                             Cl                                                                                  ##STR409##         Bluish red         206                                                                               ##STR410##                                                                                         ##STR411##                                                                             Cl                                                                                  ##STR412##         Bluish red         207                                                                               ##STR413##                                                                                         ##STR414##                                                                             Cl                                                                                  ##STR415##         Bluish red         208                                                                               ##STR416##                                                                                         ##STR417##                                                                             F                                                                                   ##STR418##         Bluish red         209                                                                               ##STR419##                                                                                         ##STR420##                                                                             Cl                                                                                  ##STR421##         Bluish red         210                                                                               ##STR422##                                                                                         ##STR423##                                                                             Cl                                                                                  ##STR424##         Bluish red         211                                                                               ##STR425##                                                                                         ##STR426##                                                                             Cl                                                                                  ##STR427##          Bluish red        212                                                                               ##STR428##                                                                                         ##STR429##                                                                             Cl                                                                                  ##STR430##         Bluish red         213                                                                               ##STR431##                                                                                         ##STR432##                                                                             F                                                                                   ##STR433##         Bluish red         214                                                                               ##STR434##                                                                                         ##STR435##                                                                             F                                                                                   ##STR436##         Bluish red         215                                                                               ##STR437##                                                                                         ##STR438##                                                                             Cl                                                                                  ##STR439##         Bluish red         216                                                                               ##STR440##                                                                                         ##STR441##                                                                             Cl                                                                                  ##STR442##         Bluish red         217                                                                               ##STR443##                                                                                         ##STR444##                                                                             Cl                                                                                  ##STR445##         Bluish red         218                                                                               ##STR446##                                                                                         ##STR447##                                                                             Cl                                                                                  ##STR448##         Bluish red         219                                                                               ##STR449##                                                                                         ##STR450##                                                                             Cl                                                                                  ##STR451##         Bluish red         220                                                                               ##STR452##                                                                                         ##STR453##                                                                             Cl                                                                                  ##STR454##         Bluish red         221                                                                               ##STR455##                                                                                         ##STR456##                                                                             Cl                                                                                  ##STR457##         Bluish red         222                                                                               ##STR458##                                                                                         ##STR459##                                                                             Cl                                                                                  ##STR460##         Bluish red         223                                                                               ##STR461##                                                                                         ##STR462##                                                                             Cl                                                                                  ##STR463##         Bluish red         224                                                                               ##STR464##                                                                                         ##STR465##                                                                             Cl                                                                                  ##STR466##         Bluish red         225                                                                               ##STR467##                                                                                         ##STR468##                                                                             F                                                                                   ##STR469##         Bluish red         226                                                                               ##STR470##                                                                                         ##STR471##                                                                             F                                                                                   ##STR472##         Bluish red         227                                                                               ##STR473##                                                                                         ##STR474##                                                                             Cl                                                                                  ##STR475##         Bluish red         228                                                                               ##STR476##                                                                                         ##STR477##                                                                             Cl                                                                                  ##STR478##         Bluish red         229                                                                               ##STR479##                                                                                         ##STR480##                                                                             Cl                                                                                  ##STR481##         Bluish red         230                                                                               ##STR482##                                                                                         ##STR483##                                                                             Cl                                                                                  ##STR484##         Bluish red         231                                                                               ##STR485##                                                                                         ##STR486##                                                                             Cl                                                                                  ##STR487##         Bluish red         232                                                                               ##STR488##                                                                                         ##STR489##                                                                             Cl                                                                                  ##STR490##         Bluish red         233                                                                               ##STR491##                                                                                         ##STR492##                                                                             Cl                                                                                  ##STR493##         Bluish             __________________________________________________________________________                                                               red            

EXAMPLE 234

The monoazo compound (92.7 parts) represented by the following formulain a free acid form, ##STR494## which had been obtained in Example 186,was dissolved in water (500 parts), and to this solution was added3-aminobenzenesulfonic acid (34.6 parts). The mixture was heated upto80° to 85° C. while controlling the pH within a range of 4 to 6 using a20% aqueous sodium carbonate solution, and then stirred for 7 hours atthat temperature and that pH. Thereafter, the reaction mixture was mixedwith sodium chloride (45 parts) to deposit crystals, which werecollected on a filter, washed and dried at 60° C. to obtain a monoazocompound of the following formula (234) in a free acid form. ##STR495##

EXAMPLES 235 to 274

Example 234 was repeated, provided that each monoazo compound shown in asecond column of the following formula, in which the monoazo compoundused is expressed in terms of each Example No., was used in place of themonoazo compound obtained in Example 186, and each compound shown in athird column in place of 3-amino -bezenesulfonic acid, thereby obtainingthe corresponding desired monoazo compounds.

    ______________________________________                                               Example No.                                                                   of Monoazo                                                             Example                                                                              compound   Compound of                                                 No.    obtained   Formula (VIII)     Shade                                    ______________________________________                                        235    142                                                                                       ##STR496##        Red                                      236    145                                                                                       ##STR497##        Red                                      237    148        H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.3 H                                                            Bluish                                                                        red                                      238    149        NH.sub.3           Red                                      239    152                                                                                       ##STR498##        Red                                      240    153                                                                                       ##STR499##        Bluish red                               241    156                                                                                       ##STR500##        Red                                      242    157        NH(CH.sub.2 CH.sub.2 OH).sub.2                                                                   Bluish                                                                        red                                      243    161                                                                                       ##STR501##        Red                                      244    164                                                                                       ##STR502##        Red                                      245    166                                                                                       ##STR503##        Bluish red                               246    168                                                                                       ##STR504##        Red                                      247    169                                                                                       ##STR505##        Bluish red                               248    173                                                                                       ##STR506##        Red                                      249    175                                                                                       ##STR507##        Bluish red                               250    177                                                                                       ##STR508##        Bluish red                               251    179                                                                                       ##STR509##        Red                                      252    180                                                                                       ##STR510##        Bluish red                               253    182                                                                                       ##STR511##        Red                                      254    185                                                                                       ##STR512##        Red                                      255    187        NH.sub.2 (CH.sub. 2 CH.sub.2 OH)                                                                 Bluish                                                                        red                                      256    188                                                                                       ##STR513##        Red                                      257    191                                                                                       ##STR514##        Red                                      258    194                                                                                       ##STR515##        Red                                      259    197        H.sub.2 NCH.sub.3  Bluish                                                                        red                                      260    200        H.sub.2 NCH.sub.2 CH.sub.3                                                                       Bluish                                                                        red                                      261    203                                                                                       ##STR516##        Bluish red                               262    204                                                                                       ##STR517##        Bluish red                               263    206                                                                                       ##STR518##        Bluish red                               264    210                                                                                       ##STR519##        Bluish red                               265    213                                                                                       ##STR520##        Bluish red                               266    214                                                                                       ##STR521##        Bluish red                               267    217        H.sub.2 NCH.sub.2 CH.sub.2 OSO.sub.3 H                                                           Bluish                                                                        red                                      268    219        H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.3                                                             Bluish                                                                        red                                      269    222                                                                                       ##STR522##        Bluish red                               270    224                                                                                       ##STR523##        Bluish red                               271    226                                                                                       ##STR524##        Bluish red                               272    229                                                                                       ##STR525##        Bluish red                               273    230                                                                                       ##STR526##        Bluish red                               274    233                                                                                       ##STR527##        Bluish red                               ______________________________________                                    

EXAMPLE 275

Example 120 was repeated, provided that2-methylamino-8-hydroxynaphthalene-3, 6-disulfonic acid (33.3 parts) wasused in place of 7-ethylamino-1-naphthol-3-sulfonic acid (26.7 parts),thereby obtaining a monoazo compound represented by the followingformula (275) in a free acid form. ##STR528##

EXAMPLES 276 to 293

Example 120 was repeated, provided that each diamine compound of theformula (II) shown in a third column of the following table was used inplace of 2-amino-5-aminomethylnaphthalene-1-sulfonic acid, each naphtholcompound of the formula (V) shown in a second column in place of7-ethylamino-1-naphthol-3-sulfonic acid, each compound of the formula(VIII) shown in a fourth column in place of methanol, and each aromaticamine compound of the formula (III) shown in a fifth column in place of1-ethylaminobenzene-4-β-sulfatoethylsulfone, thereby obtaining thecorresponding desired monoazo compounds.

         Compound of   Example Compound of Compound of Formula Compound of     No. Formula (V) Formula (II) (VIII) Formula (III) Shade             276      ##STR529##      ##STR530##      CH.sub.3      OH     ##STR531##      Red      277 "     ##STR532##      "      ##STR533##      Bluishred      278 "     ##STR534##      " " Red      279     ##STR535##      " " " "      280     ##STR536##      ##STR537##      CH.sub.3      OH     ##STR538##      Red  281 " " CH.sub.3 CH.sub.2      OH     ##STR539##      "      282     ##STR540##      ##STR541##      CH.sub.3      OH     ##STR542##      "      283 "     ##STR543##      "      ##STR544##      Bluishred      284     ##STR545##      ##STR546##      CH.sub.3      OH     ##STR547##      Red      285     ##STR548##      " " " "      286 "     ##STR549##      C.sub.2 H.sub.5 OH " Bluishred  287 " " CH.sub.3      OH     ##STR550##      Bluishred      288     ##STR551##      ##STR552##      ##STR553##      ##STR554##      Red      289 "     ##STR555##      CH.sub.3 OH " Bluishred      290 "     ##STR556##      "      ##STR557##      Red      291     ##STR558##      " " " "      292     ##STR559##      ##STR560##      CH.sub.3      OH     ##STR561##      Red      293 "     ##STR562##      C.sub.2 H.sub.5      OH " "

Dyeing Example 1

The monoazo compounds (1) and (142) obtained in Examples 1 and 142 each(0.3 part) was dissolved in water (200 parts), and sodium sulfate (20parts) and cotton (10 parts) were added thereto. The bath was heated to50° C., and then sodium carbonate (4 parts) was added thereto. Dyeingwas continued for 1 hour at that temperature. Thereafter, the cotton waswashed with water and soaped to obtain a dyed product of a deep redcolor. Both dyed products were excellent in fastness properties,particularly formalin fastness, light fastness and perspiration lightfastness, and both monoazo compounds were found to have good build-upproperty.

Dyeing Example 2

The monoazo compounds (63) and (197) obtained in Examples 63 and 197each (0.3 parts) was dissolved in water (150 parts), and sodium sulfate(30 parts) and cotton (10 parts) were added thereto. The bath was heatedto 60° C. 20 Minutes thereafter, sodium carbonate (4 parts) was addedthereto. Dyeing was continued for 1 hour at that temperature. The cottonwas washed with water and soaped to obtain a dyed product of a deep redcolor excellent in fastness properties, particularly formalin fastness,light fastness and perspiration light fastness, with good build-upproperty.

Dyeing Example 3

The monoazo compounds obtained in Examples 1 to 86 and 142 to 233 each(0.3 part) was dissolved in water (300 parts), and sodium sulfate (30parts) and cotton (10 parts) were added thereto. The bath was heated to60° C. 20 Minutes thereafter, sodium carbonate (5 parts) was addedthereto, and dyeing was continued for 1 hour at that temperature. Thecotton was washed with water and soaped to obtain a dyed product of adeep red color excellent in fastness properties, particularly formalinfastness, light fastness and perspiration fastness with good build-upproperty.

Dyeing Example 4

The monoazo compounds obtain in Examples 87 to 141 and 234 to 293 each(0.3 part) was dissolved in water (200 parts), and sodium sulfate (30parts) and cotton (10 parts) were added thereto. The bath was heated to50° C. 30 Minutes thereafter, trisodium phosphate 4 parts) was addedthereto, and dyeing was continued for 1 hour at that temperature.Thereafter, the cotton was washed with water and soaped to obtain a dyedproduct of a deep red color excellent in fastness properties,particularly formalin fastness, light fastness and perspiration lightfastness with good build-up property.

    ______________________________________                                        Dyeing Example 5                                                              Composition of color paste                                                                            Parts                                                 ______________________________________                                        Each of Monoazo compounds obtained                                                                     5                                                    in Examples 1 to 86 and 142 to 233                                            Urea                     5                                                    Sodium alginate (5%), thickener                                                                       50                                                    Hot water               25                                                    Sodium hydrogencarbonate                                                                               2                                                    Balance (water)         13                                                    ______________________________________                                    

Mercerized cotton broad cloth was printed with the color paste havingthe composition described above, and then pre-dried, subjected tosteaming at 100° C. for 5 minutes, rinsed with hot water, soaped, againrinsed with hot water, and then dried. Thus, there was obtained aprinted product of a deep red color excellent in fastness properties,particularly formalin fastness, light fastness and perspiration lightfastness with a high fixing percent and good build-up property.

    ______________________________________                                        Dyeing Example 6                                                              Composition of color paste                                                                            Parts                                                 ______________________________________                                        Each of monoazo compounds obtained in                                                                  4                                                    Examples 87 to 141 and 234 to 293                                             Urea                     5                                                    Sodium alginate (5%), thickener                                                                       50                                                    Hot water               25                                                    Sodium hydrogencarbonate                                                                               2                                                    Balance (water)         14                                                    ______________________________________                                    

Using the color paste of the above composition, a manner similar to thatof Dyeing Example 6 was repeated, provided that steaming was carried outat 120° C., thereby obtaining a dyed product like in Dyeing Example 5.

Dyeing Example 7

The monoazo compounds obtained in Examples 1 to 86 and 142 to 233 each(25 parts) was dissolved in hot water, and the solution was cooled to25° C. 32.5% Aqueous sodium hydroxide solution (5.5 parts) and 50° Be'water glass were added thereto, and water was added to make the whole1000 parts at 25° C. to obtain a padding liquor. Immediately thereafter,cotton cloth was padded with the padding liquor and batched up, and thecloth wrapped tightly with a polyethylene film was allowed to stand in aroom kept at 20° C.

Above manner was repeated to obtain a padded cotton cloth, which wasthen wrapped tightly with a polyethylene film, and allowed to stand in aroom kept at 5° C.

Bothe were allowed to stand for 20 hours, and thereafter washed withcool water and then hot water, soaped with a boiling detergent, washedwith cool water and then dried.

There was observed almost no difference in their color shade and depthbetween the dyed products obtained after standing at 5° C. and 20° C.each for 20 hours. In this cold batch-up dyeing method, each monoazocompound was found to have good build-up property.

Dyeing Exampe 8

Using the monoazo compounds obtained in Examples 87 to 141 and 234 to293, Dyeing Example 7 was repeated. Then, results similar to those ofDyeing Example 7 were obtained.

Dyeing Example 9

The monoazo compounds obtained in Examples 1 to 86 and 142 to 233 each(25 parts) was dissolved in hot water, and the solution was cooled to25° C. To this solution were added 32.5% aqueous sodium hydroxidesolution (10 parts) and anhydrous sodium sulfate (30 parts), and thenwater was added thereto make the hole 1000 parts at 25° C. Immediatelythereafter, viscose rayon woben fabric was padded with the obtainedpadding liquor. The fabric padded was batched up, wrapped tightly with apolyethylene film, and allowed to stand in a room kept at 20° C.

The above manner was repeated to obtain the fabric padded, which wasthen batched-up, wrapped with a polyethylene film and then allowed tostand in a room kept at 5° C.

Both were allowed to stand for 20 hours, and thereafter washed with coolwater and then hot water, soaped with a boiling detergent, then washedwith cool water and dried to obtain each dyed product.

There was observed almost no difference in color shade and depth betweenthe dyed products obtained after standing at 5° C. and 20° C. each for20 hours.

Dyeing Example 10

Using the monoazo compounds obtained in Examples 87 to 141 and 234 to293, a manner similar to that of Dyeing Example 9 was carried out, thenobtaining results similar to those in the above Example.

Dyeing Example 11

Dyeing Example 3 was repeated, provided that sodium carbonate was usedin an amount of 3 parts in place of 5 parts, thereby obtaining resultssimilar to those in Dyeing Example 3.

Dyeing Example 12

Dyeing Example 3 was repeated, provided that the dyeing was continued at60° C., respectively, in place of 50° C., thereby obtaining resultssimilar to those in Dyeing Example 3.

Dyeing Example 13

Dyeing Example 3 was repeated, provided that sodium sulfate was used inan amount of 15 parts in place of 30 parts, thereby obtaining resultssimilar to those in Dyeing Example 3.

Dyeing Example 14

Dyeing Example 4 was repeated, provided that water and sodium sulfatewere used in each amount of 150 parts and 23 parts in place of 200 partsand 30 parts, respectively, thereby obtaining results similar to thosein Dyeing Example 4.

What is claimed is:
 1. A monoazo compound of the following formula in afree acid form, ##STR563## wherein R₁ and R₂ independently of oneanother denote hydrogen, lower alkyl unsubstituted or substituted withhydroxy, cyano, C₁ -C₄ alkoxy, halogen, carboxy, carbamoyl, C₁ -C₄alkoxycarbonyl, C₁ -C₄ alkylcarbonyloxy, sulfo or sulfamoyl, R₃ denoteslower alkyl unsubstituted or substituted with hydroxy, cyano, C₁ -C₄alkoxy, halogen, carboxy, carbamoyl, C₁ -C₄ alkoxy, halogen, carboxy,carbamoyl, C₁ -C₄ alkoxycarbonyl, C₁ -C₄ alkylcarnoyloxy, sulfo orsulfamoyl, acetyl, propionyl, butyl, valeryl, benzoyl, or a group of theformula ##STR564## R_(denotes) hydrogen, lower alkyl unsubstituted orsubstituted with hydroxy, cyano, C₁ -C₄ alkoxy, halogen, carboxy,carbamoyl, C₁ -C₄ alkoxycarbonyl, C₁ -C₄ alkylcarbonyloxy, sulfo orsulfamoyl, and R₅ denotes hydrogen or sulfo, B denotes a group of theformula, ##STR565## in which R₆ is hydrogen, chlorine, sulfo, carboxyl,methyl, methoxy or ethoxy, or a group of the formula, ##STR566## Xdenotes chlorine, fluorine, lower alkoxy, phenoxy, unsubstituted orsubstituted with C₁ -C₄ alkyl, C₁ -C₄ alkoxy, nitro, sulfo, carboxyl orchlorine, or a group of formula ##STR567## in which R₇ and R₈independently of one another are hydrogen, lower alkyl unsubstituted orsubstituted with C₁ -C₄ alkoxy, sulfo, carboxyl, hydroxy, chlorine,phenyl, or sulfate; phenyl unsubstituted or substituted with C₁ -C₄alkyl, C₁ -C₄ alkoxy, sulfo, carboxy or chlorine; naphthyl unsubstitutedor substituted with hydroxy, carboxy, sulfo, C₁ -C₄ alkyl, C₁ -C₄ alkoxyor chlorine; or benzyl unsubstituted or substituted with C₁ -C₄ alkyl,C₁ -C₄ alkoxy, sulfo chlorine; A denotes phenylene unsubstituted orsubstituted with methyl, ethyl, methoxy, ethoxy, chlorine, bromine orsulfo or naphthylene unsubstituted or substituted with sulfo, and Zdenotes a group of the formula, --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Y, inwhich Y is a group splittable by the action of an alkali.--
 2. A monoazcompound according to claim 1, wherein R₁ and R₂ independently of oneanother denote hydrogen or methyl or ethyl, and A denotes phenyleneunsubstituted or substituted with one or two members selected frommethyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo, ornaphyhylene unsubstituted or substituted with one sulfo.
 3. A monoazocompound according to claim 1, wherein Z denotes --SO₂ CH═CH₂, --SO₂ CH₂CH₂ OSO₃ H, --SO₂ CH₂ CH₂ SSO₃ H, --SO ₂ CH₂ CH₂ OPO₃ H₂ or --SO₂ CH₂CH₂ OCOCH₃ and X denotes chlorine, ##STR568## fluorine or a group of inwhich R₉ is hydrogen or methyl or ethyl.
 4. A monoazo compound accordingto claim 1, wherein B denotes ##STR569## in which the asterisked linkageis bonded to the group ##STR570##
 5. A compound of the following formulain a free acid form, ##STR571## wherein R₅ denotes hydrogen or sulfo,R_(denotes) hydrogen, methyl or ethyl, R₁₁ denotes hydrogen, chlorine orsulfo, R₁₂ denotes methyl, ethyl, acetyl or propionyl, R₁₃ denoteshydrogen, methyl or ethyl, and Z₁ denotes --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂OSO₃ H.
 6. A compound of the following formula in a free acid form,##STR572## wherein R₅ denotes hydrogen or sulfo, R₁₀ denotes hydrogen,methyl or ethyl, R₁₁ denotes hydrogen, chlorine or sulfo, R₁₂ denotesmethyl, ethyl, acetyl or propionyl, R₁₃ denotes hydrogen, methyl orethyl, R₁₄ denotes hydrogen or sulfo, and Z₁ denotes --SO₂ CH═CH₂ or--SO₂ CH₂ CH₂ OSO₃ H.